通过邻羟基苯基膦和醛的缩合反应合成苯并氧杂磷杂环戊烯

doi:10.6023/cjoc202202012

摘要/Abstract

报道了一种利用简单易得的底物, 通过酸促进的缩合环化反应来合成2,3-二氢苯并[d][1,3]氧杂磷杂环戊烯类化合物的新路线. 该反应操作简便, 通过普通硅胶色谱即可实现反应中产生的非对映异构体的分离, 可应用于克级规模合成. 当改用联萘酚磷酸酯[(±)-BINOL-phosphoric acids]为缩合反应促进剂时, 可以实现高非对映立体选择性的构筑苯并氧杂磷杂环戊烯类化合物.

关键词: 有机磷, 苯并氧杂磷杂环戊烯, 缩合反应, 非对映选择性

A facile method to synthesize dihydrobenzooxaphospholes was developed from a p-toluenesulfonic acid (p-TSA)- promoted intermolecular cyclocondensation of the readily available 2-phosphinylphenol and aromatic aldehydes. The desired products were obtained as a mixture of stereoisomers. Interestingly, the diastereoisomers could be separated easily by flash column chromatography. The gram-scale and diastereoselective syntheses were also successfully performed.

Key words: organophosphorus, dihydrobenzooxaphosphole, cyclocondensation, diastereoselectivity

引用此文

朱雪莉, 杨绍丽, 郏彩霞, 李静, 段征. 通过邻羟基苯基膦和醛的缩合反应合成苯并氧杂磷杂环戊烯[J]. 有机化学, 2022, 42(7): 2201-2213.

Xueli Zhu, Shaoli Yang, Caixia Jia, Jing Li, Zheng Duan. Synthesis of Dihydrobenzooxaphospholes via Cyclocondensation of 2-Phosphinylphenol and Aldehydes[J]. Chinese Journal of Organic Chemistry, 2022, 42(7): 2201-2213.

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图/表 7

Scheme 1. Intramolecular cyclization to dihydro-oxaphosphole

Scheme 2. Synthesis of 2-phosphinylphenol

Entry	Acid	Solvent	Temp./℃	Time/h	Yield^b/%
1	p-TSA (2.0 equiv.)	Toluene	120	12	45+33
2	p-TSA (2.0 equiv.)	MeCN	120	12	Trace
3	p-TSA (2.0 equiv.)	1,2-Dichloroethane	120	12	48+39
4	p-TSA (2.0 equiv.)	1,2-Dichloroethane	100	12	12+Trace
5	p-TSA (2.0 equiv.)	1,2-Dichloroethane	80	12	Trace
6	p-TSA (1.0 equiv.)	1,2-Dichloroethane	120	12	9+Trace
7	p-TSA (10 mol%)	1,2-Dichloroethane	120	12	Trace
8	p-TSA (2.0 equiv.)	1,2-Dichloroethane	120	8	41+29
9	CF₃COOH (2.0 equiv.)	1,2-Dichloroethane	120	12	56+27

Table 1. Optimization of the reaction conditionsa

Table 2. Reaction scope of 4 and 5a

Scheme 3. Gram-scale reaction with 4n

Figure 1. X-ray crystal structures of trans-6o (A, CCDC: 2130832) and cis-6o (B, CCDC: 2088691) All hydrogen atoms have been omitted for the sake of clarity, and the level set for thermal ellipsoids of all atoms is 30%. Main bond lengths (nm) and angles (°): trans-6o: P(1)—C(1) 0.1792(2), P(1)—O(1) 0.14807(15), P(1)—C(13) 0.1868(2), P(1)—C(14) 0.1784(2), O(2)— C(13) 0.1452(3), O(2)—C(15) 0.1374(3), C(12)—C(13) 0.1497(3), C(14)—C(15) 0.1383(3), O(1)—P(1)—C(1) 11.240(9), O(1)—P(1)— C(13) 11.698(10), O(1)—P(1)—C(14) 11.780(10), O(2)—C(13)—P(1) 10.663(15), C(12)—C(13)—P(1) 11.524(15), C(13)—P(1)—C(14) 9.057(10), C(13)—O(2)—C(15) 11.196(17). cis-6o: P(1)—C(1) 0.1796(2), P(1)—O(1) 0.14753(18), P(1)—C(13) 0.1866(3), P(1)—C(13) 0.1866(3), O(2)—C(13) 0.1444(3), O(2)—C(14) 0.1374(3), C(12)— C(13) 0.1505(3), C(14)—C(15) 0.1379(3), O(1)—P(1)—C(1) 11.248(12), O(1)—P(1)—C(13) 11.430(12), O(1)—P(1)—C(15) 11.852(11), C(1)— P(1)—C(13) 11.004(11), C(1)—P(1)—C(15) 10.874(11), C(13)—P(1)— C(13) 9.078(12), C(14)—O(2)—C(13) 11.31(2)

Entry	Acid	Yield^b/%
1	(rac)-BINOL-phosphoric acid (2.0 equiv.)	79
2	(R)-BINOL-phosphoric acid (2.0 equiv.)	76
2	(S)-BINOL-phosphoric acid (2.0 equiv.)	62

Table 3. BINOL-phosphoric acids promoted reactionsa

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